The Chemistry of Fire

• The fire tetrahedron

• Fires can be prevented by suppression

of any one of these
Application of the Fire Tetrahedron
• Fuel-
– Shut off the natural gas supply
• Oxidizer
– Close the windows, smother the fire with a blanket
• Heat
– Pour water on the flame, use CO2 extinguisher
• Free radical chain reaction-
– Adsorb radicals with chemical suppressants, salts
 Fuels
• Organic – C, O, H and sometimes N
– Wood is 40-50% cellulose and hemicellulose
• (5 and 6 carbon sugars)
Wood tends to produce oxygenated
combustion products
 Turpenes in turpentine
Nowadays, apart from specialised grades mainly for
artists’ use (balsam turpentine) turpentine is a by-
product of the production of pulp. Sulphate
turpentine is chilled from the gas emitted when
wood chips are pre-heated with steam before
digestion. Pine and spruce have the best turpentine
yields.
Turpentine consists of 45-75% a-pinene (1), 5-30%
b-pinene (2), 2-40% 3-carene (3), other turpentines
such as limonene and camphene and their
oxidation products, such as alcohols and
aldehydes.

http://apps.kemi.se/flodessok/floden/kemamne_eng
/terpentin_eng.htm

Used in moderation, turpentine is an ideal accelerant for arson

 Other fuels
• Cotton – mostly cellulose –
• Hydrocarbons (CH2)n
 Other fuels II
• Inorganic fuels
– Mg, Al, S, Zn, etc

– Note surface area is important

• Wood dust ignites easily
• Diesel ignites in a spray, but is difficult to light in a pool
• Metals used in pyrotechnic devices are finely powdered
 Oxidizing Agents

• Usually oxygen from air

– In medical facilities can be accelerated
• Temperature greatly affects a fires need for
oxygen
– @25C need 14-16% O2
– @900-1100C flashover conditions- (spontaneous
ignition of entire room) nearly 0% oxygen is needed

• This is the effect of the flammable limit, the

upper and lower concentrations of a flammable
gas and air expressed in % fuel that can be
ignited at a specific temperature and pressure
 Types of Fire
• Flaming combustion
– Common open flame fires like
gas burners
– Gas to gas reaction, fuel must
be in gaseous state
– Liquids and solids don’t burn in
an open flame
– these must undergo chemical
or phase change first
– Oxygen must be above 10%
 Smoldering Combustion
• Glowing combustion
occurs without the
generation of flames
– It is a solid to gas reaction
– Surface of solid reacts
directly with oxidizer
– Often due to a deficiency
of oxidizer
– Less than 10% oxygen is
needed
 Partial or incomplete combustion
• Stoichiometric ratios are rarely involved in
combustion
– Oxidation reactions often don’t go to
completion
– This is called incomplete combustion
• C4H10 + 13/2 O2 
 Types of Fire
• Flaming combustion
– Common open flame fires like
gas burners
– Gas to gas reaction, fuel must
be in gaseous state
– Liquids and solids don’t burn in
an open flame
– these must undergo chemical
or phase change first
– Oxygen must be above 10%
 Smoldering Combustion
• Glowing combustion
occurs without the
generation of flames
– It is a solid to gas reaction
– Surface of solid reacts
directly with oxidizer
– Often due to a deficiency
of oxidizer
– Less than 10% oxygen is
needed
 Flammable limits
• Fuel/air ratio must be correct for combustion to occur
• There is a minimum and maximum level
– Measured at 0 C and 1 ATM

– Gasoline -1.4 - 7.6% in air

– Acetylene- 4-100%
– H2 4-75%

– – for this reason it is practically impossible for a full or partly full

gas tank to explode or even burn

– The danger comes as temperature increases causing the range

of flammable limits to expand

– http://www.youtube.com/watch?v=NOTWg3Krww0
 Examples
• Flash point
– http://www.youtube.com/watch?v=yE5LdCyN0aE&fea
ture=related
• Flammable limit
– http://www.youtube.com/watch?v=ICsvddmYMr4
• Auto ignition
– http://www.youtube.com/watch?v=lFIiTxqolZk
• Backdraft
– http://www.youtube.com/watch?v=91R6MLcf-WQ
 Partial or incomplete combustion
• Stoichiometric ratios are rarely involved in
combustion
– Oxidation reactions often don’t go to
completion
– This is called incomplete combustion and
results in formation of carbon monoxide.

Complete vs incomplet combustion in a gas pilot light

 Effect of Fuel on a Fire
• Fires have either excess air or excess fuel
 Effect of venting
• Venting a fire has important effects
– Gases inside a room may be oxygen starved
– Gases venting to outside may ignite
– Gases venting into an enclosed room will not
spread a fire

– Opening doors and windows may cause a

smoldering fire to reignite
 Heat
• Sufficient heat is required to produce a transition from solid
to liquid to vapor phase – only vapors burn
• Additional energy is also required to initiate the chemical
reaction

• Once initiated such reactions are exothermic with a large

increase in entropy
 Initiation of Fire
• The heat required to initiate a fire is a
critical step
– Matchespaperstickswood
– Each step is critical and the underlying
process is to get the wood hot enough that it
produces volatile gases that burn.
 Types of ignition
• Spontaneous ignition
– Chemical or biological processes that create
sufficient heat to ignite the reacting material
– Basically heat is produced faster than it can
be dissipated.
– Common with vegetable oils, hay
Spontaneous combustion of
hay in a barn
 Auto-ignition
• Ignition of a material in the absence of
flame or spark (non-piloted ignition)
• All combustible materials must reach their
autoignition temperature to burn
– Thus one could light paper two ways:
• Use a match to heat a small section to ignition
• Heat the entire piece of paper in an oven.
 Flash Point
• There is a temperature above which a fuel will
flash when presented with a flame – this is the
flash point
• @ 10-20 degrees above the flash point there is
sufficient vapor pressure to sustain a flame
• The auto-ignition temperature is the temperature
of spontaneous ignition
– For kerosene, the flash point is 100F and the ignition
temperature is 410F.
 Chemical Chain Reactions
• Reactions become self sustaining when sufficient heat
from exothermic reactions radiates back to cause ignition
away from source
• The burning process involves pyrolysis, the breakdown
of solids to produce gases and free radicals
 Removal of Free Radicals
• Halon fire extinguishers work by shutting
down the propagation of radicals

Bromine and chlorine quickly shut down

free radicals
 Types of fire extinguishers
• Type A - Water/firehoses
– Cools fire as water converts to steam
– Causes damage and is dangerous in electrical and metal fires
• Type BC - Powder extinguishers
– 80% NaHCO3
– Starve oxygen and cool by release of CO2
– 6-8 meter range
• Type BC - CO2 gas extinguishers
– Leave no residue for expensive cleanup
– Cool fire and remove oxygen
– 1.5 meter range- can be dangerous for large electrical fires, esp if visibility is
limited due to smoke
• Type ABC – Ammonium Phosphate
– Releases ammonia which removes oxygen and yields phosphoric acid
which induces char which releases fewer volatiles
• Type ABC Halon
– Eliminates free radicals, displaces oxygen
• Type D fire extinguisher
– A bucket of sand for metal fires
Fires are classified according to the material, which is being burned. The four
classes of fires, with the American and International symbols, are as follows:

Class A:
Ordinary Combustibles - Cloth, Wood, Paper, Rubber, many plastics.

Extinguisher:
Pressurized water (it removes Heat) suitable for use on Class A only. Dry
chemical: mono-ammonium phosphate, (it removes contact between Oxygen
and Fuel), rated for Class A, B, and C fires.
Extinguishers suitable for Class A fires should be identified by a green triangle
containing the letter "A" and the pictograph shown above.

http://www.fireadesource.com/faqs.html
Class B:
Flammable Liquids - Gasoline, Oil, Oil-based paint,
Cooking Oil

Extinguisher:
1) Carbon dioxide (it displaces Oxygen but dissipates quickly; the combustible
surface, if hot, may re-ignite).
2) Dry Chemical (it removes Oxygen from the Fuel by coating the surface inhibiting
the release of combustible vapors): mono ammonium phosphate, rated for Class A,
B, and C fires; Sodium Bicarbonate and Potassium Bicarbonate, for Class B and C,
preferred for cooking oil fires.
3) Halon: it interferes with the fire chemical reaction by quenching free radicals.
Production has been banned (Montreal, 1998) because Halon has been found to be
an ozone-depleting substance.
Extinguishers that are suitable for Class B fires are identified by a red square
containing the letter B and the pictograph shown above.

http://www.fireadesource.com/faqs.html
 Class C:
Energized electrical equipment, including appliances, wiring, circuit
breakers, and fuse boxes.

Extinguisher:
1) Carbon dioxide (it removes Oxygen but dissipates quickly; the combustible surface,
if still hot, may re-ignite).
2) Dry Chemical (it removes Oxygen from the Fuel by coating the surface and
inhibiting the release of combustible vapors): mono Ammonium Phosphate, rated for
Class A, B, and C fires; Sodium Bicarbonate and Potassium Bicarbonate, for Class B
and C, preferred for cooking oil fires.
3) Halon: it interferes with the fire chemical reaction by quenching free radicals.
Production has been banned (Montreal, 1998) because Halon has been found to be
an ozone-depleting substance.
Extinguishers suitable for Class C fires are identified by a blue circle containing the
letter C and the pictograph shown above.

http://www.fireadesource.com/faqs.html
Class D:
Combustible metal such as Mg, Na, Li, powdered Al, etc.

Extinguisher:
Extinguishers rated for class D fires have a label, which list the types of metal,
on which the extinguisher may be used. The extinguishing medium must not
react with the burning metal. Extinguishers suitable for Class D fires are
identified by a yellow star containing the letter D.

http://www.fireadesource.com/faqs.html
 Fire Retardants
• Barrier theory- chemicals form a glassy barrier on exposure to heat

• Thermal theory – chemicals change the thermal property of the wood to dissapate
(conduct) or absorb (heat capacity)heat - sodium silicates, chemicals with waters of
hydration

• Noncombustable gas theory – chemicals release nonflamable gases interfering with

combustion - borax (soduim tetraborate decahydrate) releases large quantities of
water following pyrolysis

• Free radical trap theories – chemicals release free radical inhibitors at pyrolytic
temperatures interrupting chain propagation – halogens attack free radicals formed

• Increased char theories – temperature of pyrolysis is lowered, directing degradation

towards charring instead of burning, lower volatile gases – borax, NH3PO4

• Most fire retardants operate using several of these mechanisms

(H2O) x10
NH3 H2P04
Levan, Chemistry of Fire Retardancy in The Chemistry of Solid Wood
http://www.fpl.fs.fed.us/documnts/pdf1984/levan84a.pdf
 Heat Transfer
• Three mechanisms
– Conduction, convection, radiation
• Conductive heating
– Takes place within solids
– Rate is dependant on
» Thermal conductivity heat transfer within a material
» Heat capacity heat required to raise the
temp of a substance 1 degree C
» Density g/cm3
 Thermal Conductivity
• Thermal intertia  density, heat capacity,
thermal conductivity
– At equilibrium, density and heat capacity
become unimportant
– Thermal conductivity rules
• Pipes and metal fittings produce fire spread and
structural damage
– Thus thermal intertia is maintly important in
the early stages of a fire
 Thermal properties of selected
materials
material Thermal Density Heat
conductivity kg/m3 capacity
W/mK J/kgK
copper 387 8940 380
concrete 0.8 1900 880
pine 0.14 640 2850
polyethylene 0.35 940 1900

NFPA 921-14
 Convection
• Transfer of heat energy through the movement
of liquids or gases
• Heat is then transferred to a cooler solid
– Rate is a ftn of
• Temperature
• Surface area
• Velocity of gases
– Convection is extremely important in the early stages
of a fire
• Hot gases rise to upper portions of the room
• Then they mushroom down
• As heat builds, flashover occurs and entire room ignites
• Hot gases then spread fire through the rest of the building
 Radiation
• Transfer of heat through infrared energy
• Radiative power = σ(T)4
– where σ = 5.67 x 10-8 (watts/m2)/K4
– Stefan’s law of radiation

• Thus

• Radiative power becomes highly significant at

elevated temperatures
 Fire development
• There is a sequence of events which begin
as a fire evolves
1. Incipient stage
2. Ceiling layer development
3. Preflashover -
4. Flashover
5. Post flashover

Not all fires will go through the entire process

 Incipient phase
• Incipient – room doesn’t heat
– Can be short time – accellerant
– Or long- spontaneous combustion
• Oily rags (linseed oil) dust or even grass clipping
• Build up of heat due to chemical or bacterial action
– For ignition to occur material must be
• In a gaseous state
• At sufficient concentration to form a flammable air/gas
mixture
• Exposed to activation energy of
– Match, spark, friction
 Incipient stage
• Small flames
progress upwards
and produce hot
gases.
• Smoke begins to
accumulate
• Average
temperature is just
above ambient
 Emergent Smolder
• Fuel vapors must be raised to higher than ignition temperature
• Some solid materials begin to burn by smoldering
– A hazardous situation as incomplete combustion  release of
CO and other toxins
– Smoldering is a pyrolytic process in which chemical bonds begin
to break, gases are released and free radicals form
 Growth (open burning)
• Room begins to heat up
• Oxygen concentration still high or unchanged
• Fire burns up and out as it moves across the ceiling looking for a
way up
 Ceiling layer development
• Also called the growth
phase.
• Smoke increases and
begins to accumulate at
the ceiling level
• Room heats up and other
items begin to burn
• Hot smoke creates a
negative pressure in the
room.
• There is essentially two
layers of heat in the room,
a hot upper layer and a
cooler rest of the room.
 Preflashover
• Smoke and hot gas layer at
ceiling reaches 400-500 C
• Rate of heat transfer
increases
• Burning rate is fuel controlles
and sufficient oxygen is
present
• Items in the room begin to
pyrolyze – notice smoke
given off by chair
 Flashover
• Temperature in the room rises to the point that all materials spontaneously
combust
• Flashover can simulate arson fire as multiple points in the room ignite
• Windows break due to thermal stress, Floor to ceiling charring will occur due
to radiative heating of all exposed surfaces
• Freeburning occurs until ventilation is limited
• Fires can selflimit if nearby fuel isnt present of it initial fire is too small to
ignite adjacent materials
 Flashover
• Hot gas reached a critical
temperature of 600 C and
ignites, significantly
increasing the radiant heat
transferred to floor
• Whole room is suddenly and
completely engulfed in flame
• Transition lasts only a few
seconds
 Full Room Invovement  Ventilation Control
Backdraft
• Room transitions to oxygen regulated smoldering
– The point at which the amount of O2 regulates the fire
– Fire itself is slow smoldering producing large amounts of CO
– If a door is opened at this point, hot CO combines explosively
with O2
• Effect can be confused with explosives however char pattern
will occur only at the top of the room
 Example: Station Nightclub Fire simulation by NIST
http://www.youtube.com/watch?v=IxiOXZ55hbc

The Station nightclub fire occurred beginning at

11:07 PM EST, on Thursday, February 20, 2003, at
The Station, a glam metal and rock n roll themed
nightclub located at 211 Cowesett Ave in West
Warwick, Rhode Island, United States; it is
considered to be the fourth deadliest nightclub fire
in American history, killing 100 people, four of whom
died after being admitted to local hospitals. The fire
was caused when pyrotechnic sparks, set off by the
tour manager of the evening's headlining band,
Great White, ignited flammable sound insulation
foam in the walls and ceilings around the stage,
creating a flash fire that engulfed the club in 5½
minutes. Some 230 people were injured

At first, there was no panic. Everybody just kind of turned. Most people still just stood
there. In the other rooms, the smoke hadn't gotten to them, the flame wasn't that bad, they
didn't think anything of it. Well, I guess once we all started to turn toward the door, and we
got bottle-necked into the front door, people just kept pushing, and eventually everyone
popped out of the door, including myself
 Incipient phase
• Incipient – room doesn’t heat
– Can be short time – accellerant
– Or long- spontaneous combustion
• Oily rags (linseed oil) dust or even grass clipping
• Build up of heat due to chemical or bacterial action
– For ignition to occur material must be
• In a gaseous state
• At sufficient concentration to form a flammable air/gas
mixture
• Exposed to activation energy of
– Match, spark, friction
 Emergent Smolder

• Fuel vapors must be raised to higher than

ignition temperature
• Some solid materials begin to burn by
smoldering
– A hazardous situation as incomplete
combustion  release of CO and other toxins
– Smoldering is a pyrolytic process in which
chemical bonds begin to break, gases are
released and free radicals form
 Flashover
• Temperature in the room rises to the point
that all materials spontaneously combust
• Flashover can simulate arson fire as
multiple points in the room ignite
• Freeburning occurs until ventilation is
limited
• Fires can selflimit if nearby fuel isnt
present of it initial fire is too small to ignite
adjacent materials
 Post flashover
• Also called full room
involvement
• Every piece of
combustable material in
room burns
• Areas under furniture
may be relatively spared,
also materials near the
influx of oxygen
http://faberc.org/Images/NIST/Flashoverx3/
• Examples LivingRoomFlashover.wmv

http://faberc.org/Images/NIST/Flashoverx3/
ScotchPine.wmv
 Backdraft
• Oxygen regulated smoldering
– The point at which the amount of O2 regulates
the fire
– Fire itself is slow smoldering producing large
amounts of CO
– If a door is opened at this point, hot CO
combines explosively with O2
• Windows will blow out
• Effect can be confused with explosives however
char pattern will occur only at the top of the room
 Accelerated vs Nonaccelerated
fires
• Originally thought that accelerated fires would burn
hotter. This is not true
• Actually modern homes are composed of a lot of plastic,
which basically burns just like gasoline. (also gasoline
burns at the same temperature as wood)
• Only real difference is a faster rate of room temperature
increase. This is due to the faster rate of heat release
with gasoline
 Effects of Fire/Scene
Reconstruction
• Damage to ceiling is 5x that of Floor
• Damage is usually heaviest near origin
– Aligator char is deepest
– Scales are smaller
• Char burn rate = 1” in 40 min @1400-1600 F
– Glass melts @1200F  becomes running @1600F
• Ovid cracks in glass rapid heating
• Verticle cracks  slow fire
– Light bulbs above 40W will expand towards origin due
to melting and expansion of gas inside bulb
– Burn patterns can help indicate origin
 Liquid fuel properties
• Melting and boiling points
– Increase with number of carbons within HC class
– Branching and cyclic groups decrease melting and
boiling points (increased disorder)
– Double bonds decrease melting and boiling points
– Aromaticity increases melting and boiling points due
to increased polarity
– Alcohol groups greatly increase melting and boiling
points
 BP 254

BP 229 alcohol
BP 183
aromatic

BP 174

BP 181
cyclic
BP160 branched BP 171 alkene

BP 171
BP 148
 Specific Gravity
• Compounds lighter than water have lower
specific gravity gm/cc = 1 for H2O
• Petroleum products generally have a low
specific gravity and float on water (up to
asphalt)
• General trends-
– Increasing with carbon number for n-alkanes
– Aromatics tend to have higher SG than
alkanes
– Compounds with Cl or S tend to have high SG
 Vapor density
• Volume of vapor or gas compared to air
(Air = 29 g/mol = vapor density of 1)
– Air is 78.1% N2, 21% O2, 1% Ar, 0.03% CO2
– This is 21.9g/mol N2 6.7 g/mol O2

• If the vapor density of a gas is below 1 it

will rise. If above 1 if settles at floor level
 Vapor Density
• Only 14 gases and vapors have a vapor
density less than 1
– acetylene, ammonia, CO, diborane, H2, He,
HCN,HF, CH4, methyl lithium, Ne, N2, H2O
– 9 are flammable,
• Many other gases are heavier than air –
– Methanol, propane, butane, acetone,
pentane, toluene, etc.
 Effect of vapor density

Too Rich

Combustion possible

Too lean

Stove
 Flammability limits
Lower flammability limit upper flammability limit
• Methane 5.3% 14%
• Propane 2.2% 9.5%
• Acetylene 2.5% 81%
• Butane 1.9% 8.5%
• Gasoline 1.5% 7.6%
• Kerosene 1% 5%
• Diesel 0.5% 4.1%
• Carbon monoxide 12.5% 74%
• H 4% 75%
• HS 4.3% 45%
• NH3 15.5% 45.5%
 Vapor pressure of a liquid
mixture

• How to calculate if in an explosion LFL

was reached?
• Use Raoult’s law
– Ptotal = Sum(Pn χn)
– vapor pressure of mixture time sthe molar
fraction of the liquid in the mixture
 Flash Point calculations
• Flash point is the lowest temperature at which a
substance produces sufficient vapor to form an ignitable
mixture (pilot light)
• Gas ignites and then extinguishes. The concept is
important as this is the lowest temperature at which a
risk of fire exists.
• Flash points are temperature dependent
• 1000/(Tf+273) = B0 + B1log P25
• Where B0 and B1 are constants (see book) and P25 is
the vapor pressure at 25C
 Summary of concepts
• Melting point
• Boiling point
• Specific gravity
• Vapor density
• Flammability limits –lFL, UFL
• Vapor pressure
• Flash point – will pop
• Fire point – sustains a fire
• Ignition temperature – will ignite
• Autoignition temperature – will ignite with no source
 Thermal Conductivity
• Thermal intertia  density, heat capacity,
thermal conductivity
– At equilibrium, density and heat capacity
become unimportant
– Thermal conductivity rules
• Pipes and metal fittings produce fire spread and
structural damage
– Thus thermal intertia is maintly important in
the early stages of a fire
 Thermal properties of selected
materials
material Thermal Density Heat
conductivity kg/m3 capacity
W/mK J/kgK
copper 387 8940 380
concrete 0.8 1900 880
pine 0.14 640 2850
polyethylene 0.35 940 1900

NFPA 921-14
 Convection
• Transfer of heat energy through the movement
of liquids or gases
• Heat is then transferred to a cooler solid
– Rate is a ftn of
• Temperature
• Surface area
• Velocity of gases
– Convection is extremely important in the early stages
of a fire
• Hot gases rise to upper portions of the room
• Then they mushroom down
• As heat builds, flashover occurs and entire room ignites
• Hot gases then spread fire through the rest of the building
 Radiation
• Transfer of heat through infrared energy
• Radiative power = σ(T)4
– where σ = 5.67 x 10-8 (watts/m2)/K4
– Stefan’s law of radiation

• Thus

• Radiative power becomes highly significant at

elevated temperatures